A new molecular Br2-catalyzed polymerization of 2,5-dibromo-3,4-ethylenedioxyselenophene (DBEDOS), 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT), and their analogues, providing metal free and virtually defect free conducting polymers under mild reaction conditions. The resulting poly­(3,4-ethylenedioxyselenophene) (PEDOS), poly­(3,4-ethylenedioxythiophene) (PEDOT) and their analogues are electroactive, highly conducting and shown optoelectronic properties practically identical to electrochemically prepared insoluble thin films. This polymerization is a rare example of metal free polymerization which lead to the formation of conjugated polymer. Details characterizations of the obtained polymers were carried out and spectroelectrochemistry of PEDOS-C12 film obtained by Br2-catalyzed polymerization suggest higher conductivity and transparency compared to PEDOS-C12 film obtained by other methods.

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